Water-insoluble ethyl cellulose and plasticizer anhydrous aerosol hair lacquer



WATER-INSOLUBLE ETHYL CELLULOS E AND PLASTICIZER ANHYDROUS AEROSOL HAIRLACQUER Herman G. Philips, Jr., Wilmington, Del., assignor to HerculesPowder Company, Wilmington, Del., a corporation of Delaware v NoDrawing. Application June 7, 1954 Serial No. 435,067

8 Claims. (Cl. 167--87.1)

Patented Oct. 21, 1958 parent, therefore, that a hair-dressing lacquerof the aerosol type must meet a rather exacting combination ofrequirements to be considered satisfactory. Unfortunately, theserequirements are seldom satisfied by previously proposed hair-dressinglacquer compositions.

Now in accordance with this invention, it has been found that highlysatisfactory aerosol hair-dressing lacquers are provided by compositionscontaining as essential ingredients from about 0.5 to about 3 parts byweight of ethyl cellulose having an ethoxyl content between about andabout by weight, from about 0.5 to about 3 parts of a water-sensitiveethyl cellulose plasticizer, from about 15 to about 65 parts of a loweraliphatic alcohol having .from 1 to 3 carbon atoms in the molecule, andfrom about 35 to about 80 parts of a pressure-generating solvent of thegroup consisting of dichlorodifluoromethane and mixtures ofdichlorodifiuoroethane and 1,1,1-trichloromonofluoroethane containing atleast about 30% by weight of dichlorodifluoromethane, the combinedweight of ethyl cellulose and water-sensitive plasticizer in saidlacquer being between about 1 and about 5% by weight, and the ratio ofethyl cellulose to water-sensitive plasticizer being between about 50:50and about 85:15 by weight.

scope of the invention are given in the following table:

Ingredients Examples Ethyl cellulose (48.3% ethoxyl9.7 cp. viscosity).2. 5 1. 9 1 9 1 9 1. 9 1 9 1 9 Ethyl cellulose (49.9% ethoxyl8.9 cp.viscosity). 2. 5 Diethylene glycol monoleate 1.5 1.5 1 5 1.1 1 1 1 1Triethyl citrate Glycerin l N onytl phcnol-ethy ne oxide condensationprodc Ethylalcohol (2115512551:I: 4s 4s 46 47 47 37 47 47 47Dichlorodifiuoromethane 50 50 50 50 25 30 50 50 50Trlchloromonofluoroethane 25 30 All figures in columns 1-9, inclusive,represent parts by weight.

purpose than permanent wave compositions and are clearly distinguishablethereover. More specifically, permanent wave compositions are almostinvariably water solutions or suspensions of substances which arebrushed or combed into the hair, after which the hair is curled, set andotherwise dressed, and upon drying the hair assumes a more or lesspermanent set and style of dress. The drying process to develop thepermanent set requires a relatively long period of time. Hair-dressinglacquers, on the other hand, are intended for spray application to theouter strands of hair, after the hair has been permanently waved,brushed, combed, or otherwise dressed, to retain the hair in itspreviously dressed condition. Such lacquers provide a substantiallyinvisible hair net which holds the locks and outer strands of hairtogether, and thus enhance and preserve the dressed condition of thehair.

To serve their purpose effectively, hairdressing lacquer compositionsmust be very fast evaporating in contrast to permanent wave compositionsand must have good adhesion to human hair without imparting stickinessor brittleness thereto. They should enhancev the natural sheen of thehair, rather than have a dulling effect, and

they should be easily removed from the hair upon nor- Formulation ofsatisfactory aerosol hair-dressing lacquers in accordance with thisinvention requires the proper selection of (l) ethyl cellulose, (2)suitable ethyl cellulose modifiers or plasticizers, (3) suitable ethylcel lulose solvents, and (4) suitable pressure-generating solvents orpropellants, each within certain specified limits and proportions, asset forth hereinafter.

The ethyl cellulose used in the compositions will have an ethoxylcontent between about 45% and about 50%, and preferably between about47% and about 49%, by weight. Within this range of ethoxyl content,ethyl cellulose exhibits optimum solubility in the mixture of solventsand propellants found necessary for the practice of this invention andalso retains optimum solubility upon evaporation of the propellantcomponent of the compositions. Although any of the commerciallyavailable viscosity types of ethyl cellulose can be employed, it ispreferred to use the lower viscosity types having viscosities of about25 cps. or less as determined on 5% by weight solutions in :20toluene:ethyl alcohol at 25 C. Compositions in accordance with thisinvention will contain between about 0.5 and about 3 parts, and

quire the use of a water-sensitive plasticizer or modifier for the ethylcellulose, and any water-sensitive ethyl eel practicing this inventionlulose plasticizer or mixture of plasticizers can be employed, asdesired. Many such materials are known, and those skilled in the art arewell acquainted with them. All Water-sensitive e'thyl celluloseplasticizers are characteristically hydrophilic by'nature and have amarked afiinity for water. Typical water-sensitive ethyl celluloseplasticizers include by way of example, but not in limitation, glyceryltriac'etate, sorbitol propionate, mannitol propionate, triethylphosphate, polyhydric alcohols such as ethylene glycol, diethyleneglycol, polyethylene glycol, propylene glycol, dipropylene .glycol,tripropylene glycol, polypropylene glycol, glycerol, and the like,partial fatty acid esters of polyhydric alcohols such as glyceryldiacetate, ethylene glycol monostearate, diethylene glycol monolaurate,diethylene glycol monoleate, alkyl esters of hydroxy fatty acids such astriethyl citrate, triethyl carballylate, triethyl aconitate, dimethyltartrate, dipropyl tartrate, alkylated phenol-ethylene oxidecondensation products such as nonyl phenol-ethylene oxide, or tertiarybutyl phenol-ethylene oxide condensates, polyoxyethylated fattyalcohols, and polyoxyethylated vegetable oils. It is presently preferredto employ materials such as diethylene glycol monoleate, triethylcitrate, or nonyl phenol-ethylene oxide condensates as thewater-sensitive ethyl cellulose plasticizers.

Compositions in accordance with this invention will contain betweenabout 0.5 and about 3 parts by weight of water-sensitive ethyl celluloseplasticizer. However, an important relationship which must be adhered toin is the ratio of ethyl cellulose to water-sensitive plasticizer, whichratio must be maintained between about 50:50 and about 85:15 by weight.It will be apparent, of course, that film softness and suppleness willincrease as the proportion of water-sensitive plasticizer to ethylcellulose increases within the limits set forth. Generally, optimumresults have been obtained employing ratios of ethyl cellulose ofwatersensitive plasticizer between about 60:40 and about 70:30 byweight. The combined weight of ethyl cellulose and water-sensitiveplasticizer in the aerosol hair-dressing lacquers of this invention willbe between about 1% and about 5%, and preferably between about 1% andabout 3%, by weight, based on the total composition.

It is highly important that the ethyl cellulose solvent in thecompositions of this invention be limited to a lower aliphatic alcoholhaving from 1 to 3 carbon atoms in the molecule, as exemplified bymethyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol.Preferably these alcoholic solvents should be substantially free ofwater, as exempified by 200 proof ethyl alcohol which is the preferredethyl cellulose solvent. However, these alcoholic solvents can containsmall amounts of Water, up to about 8% by weight, particularly if thevalve and aerosol dispenser are made of corrosion-resistant materialssuch as nylon in the case of the valve, or aluminum in the case of thedispenser. From about parts to about 65 parts by weight of a loweraliphatic alcohol as set forth above will be employed in thecompositions of this invention.

Between about 35 parts and about 80 parts by weight of apressure-generating solvent or propellant will be employed in thecompositions of this invention. The pressure-generating solvent can beeither dichlorodifluoromethane alone or mixtures ofdichlorodifluoromethane and l,l,l-trichloromonofluoroethane containingat least about 30% by weight of dichlorodifiuoromethane.

It will be understood, of course, that the aerosol hairdressing lacquersof this invention can contain the usual small amounts of variousoptional ingredients such as perfumes, antiseptics, emollients,bleaching agents, coloring agents, and the like, as desired, withoutdeparting from the spirit or scope of the invention.

The compositions of this invention may be conveniently prepared bycharging the ethyl cellulose, water-sensitive plasticizer and alcoholsolvent to an uncapped aerosol container or dispenser which is thencooled by refrigeration to a temperature below the boiling point of thepressure-generating solvent. The pressure-generating solvent is thenadded as a liquid to the refrigerated mixture, the aerosol dispenser iscapped, the charged dispenser is allowed to return to room temperature,and the contents of the dispenser are agitated or tumbled to obtain asolution. Alternately, the ethyl cellulose, water-sensitive plasticizerand alcoholic solvent can be mixed together at room temperature to forma lacquer which is then charged to an uncapped aerosol dispenser andrefrigerated below the boiling point of the pressure-generating solvent,after which the pressuregenerating solvent is added as a liquid, thedispenser is capped and allowed to come to room temperature.- It is alsopossible to charge an uncapped aerosol dispenser at room temperaturewith a lacquer containing the "ethyl cellulose, water-sensitiveplasticizer and alcoholic solvent, cap the dispenser, and then pump therequisite amount of pressure-generating solvent under pressure at roomtemperature into the capped dispenser through the valve mechanism. Othervariations will be apparent to those skilled in the art.

What I claim and desire to protect by Letters Patent is:

1. A substantially anhydrous aerosol hair-dressing lacquer of thepressure-generating solvent type containing as essential ingredients ina single phase mixture from about 0.5 to about 3 parts by weight ofwaterinsoluble organosoluble ethyl cellulose having an ethoxyl contentbetween about and about by weight, from about 0.5 to about 3 parts byweight of a water- 'sensitive ethyl cellulose plasticizer, from about 15to about parts by weight of a lower aliphatic alcohol having from 1 to 3carbon atoms in the molecule, and from about 35 to about parts of apressure-generating solvent of the group consisting ofdichlorodifluoromethane and mixtures of dichlorodifluoromethane and1,1,1- trichloromonofluoroethane containing at least about 30% by weightof dichlorodifluoromethane, the combined weight of ethyl cellulose andwater-sensitive plasticizer in said lacquer being between about 1% andabout 5% by weight, and the ratio of ethyl cellulose to water-sensitiveplasticizer being between about 50:50 and :15 by weight.

2. An aerosol hair-dressing lacquer in accordance with claim 1 whereinthe water-sensitive plasticizer is diethylene glycol monoleate.

3. An aerosol hair-dressing lacquer in accordance with claim 1 whereinthe water-sensitive plasticizer is triethyl citrate.

4. An aerosol hair-dressing lacquer in accordance with claim 1 whereinthe water-sensitive plasticizer is the reaction product obtained bycondensing nonyl phenol with ethylene oxide.

5. An aerosol hair-dressing lacquer in accordance with claim 1 whereinthe water-sensitive plasticizer is ethylene glycol.

6. An aerosol hair-dressing lacquer in accordance with claim 1 whereinthe water-sensitive plasticizer is glyceryl triacetate.

7. An aerosol hair-dressing lacquer in accordance with claim 1 whereinthe lower aliphatic alcohol is 200 proof ethyl alcohol.

8. A substantially anhydrous aerosol hair-dressing lacquer of thepressure-generating solvent type containing the following essentialingredients in a single phase mixture:

p Parts by Weight Water-insoluble organosoluble ethyl cellulose (about48% ethoxyl, about 10 cp. viscosity) About 2 (l teferen ces on followingpage) References Cited in the file of this patent UNITED STATES PATENTSBennett Jan. 10, 1939 Powers Sep. 24, 1940 Medl Nov. 14, 1944 FOREIGNPATENTS France Dec. 24, 1952 6 OTHER REFERENCES

1. A SUBSTANTIALLY ANHYDROUS AEROSOL HAIR-DRESSING LACQUER OF THEPRESSURE-GENERATING SOLVENT TYPE CONTAINING AS ESSENTIAL INGREDIENTS INA SINGLE PHASE MIXTURE FROM ABOUT 0.5 TO ABOUT 3 PARTS BY WEIGHT OFWATERINSOLUBLE ORGANOSOLUBLE ETHYL CELLULOSE HAVING AN ETHOXYL CONTENTBETWEEN ABOUT 45% AND ABOUT 50% BY WEIGHT, FROM ABOUT 0.5 TO ABOUT 3PARTS BY WEIGHT OF A WATERSENSITIVE ETHYL CELLULOSE PLASTICIZER, FROMABOUT 15 TO ABOUT 65 PARTS BY WEIGHT OF A LOWER ALIPHATIC ALCOHOL HAVINGFROM 1 TO 3 CARBON ATOMS IN THE MOLECULE, AND FROM ABOUT 35 TO ABOUT 80PARTS OF A PRESSURE-GENERATING SOLVENT OF THE GROUP CONSISTING OFDICHLORODIFLUOROMETHANE AND MIXTURES OF DICHLORODIFLUOROMETHANE AND1,1,1TRICHLOROMONOFLUOROETHANE CONTAINING AT LEAST ABOUT 30% BY WEIGHTOF DICHLORODIFLUOROMETHANE, THE COMBINED WEIGHT OF ETHYL CELLULOSE ANDWATER-SENSITIVE PLASTICIZER IN SAID LACQUER BEING BETWEEN ABOUT 1% ANDABOUT 5% BY WEIGHT, AND THE RATIO OF ETHYL CELLULOSE TO WATER-SENSITIVEPLASTICIZER BEING BETWEEN ABOUT 50:50 AND 85:15 BY WEIGHT.